Coated materials and method of producing same



cannot be used to'eifectively 'or wet fish and the face coating composition prior to the Patented it... 2, 1936 cos-rm) m DuPont V N. Y a

No Drawing.

cellophane corporation and;

AND IIHIOD OI 'IEBIALS rnonncmc. s un John G. Siemllm mm H. 00mm.

of Delaware Application November 21, m0,

Y w Inc-,NewIork.

sum No- 19 Glaimr- (o 11-48) This invention relates to coated materials and method of producing same.) it relates to sheets .or films of regenerated cellulose rendered resistant to the penetration of moisture and water vapor therethroughto a substantial degree and to the process of preparing same, said materials also being transparent, flexible, non-tacky, non-odorless and capable of use as wrapping tissues. 1

Sheets or films of regenerated cellulose have found extensive use as wrapping tissues. By reason of their transparency, packages of marked beauty are obtained. These sheets, however, are not resistant to the penetration of moisture or water vapor therethrough. They, therefore, wrap products, such as bread, cake, cigars, fruits or other products which are susceptible to gain or loss of moisture and which are desired to be maintained in their substantially original riod of time. A wrapping this object, viz., the retention moisture present in the product and the prevention of moisture from the atmosphere or otherwise contacting therewith, has already been produced by treating sheets or films of regenerated cellulose with a surface coating composition in-" cluding a cellulose derivative, a gun or resin. a wax and a plasticizer. Such a material produces excellent results when used as a. wrapping tissue for breads, cakes, fruits and the like. It

found that in wrapping products having an exceedingly high moisture or water content, such as ice cream, butter, frozen like, there is a tendency after a prolonged period of time for the surface coating to become loose. Inasmuch as the base is not resistant to the passage or penetration of moisture and watergvapor therethrough, the effectiveness of the wrapper is materially impaired.

, I have found that I can overcome the abovementioned defects and prepare a product, which is resistant to the passage or penetration of moisture and water vapor, transparent, flexible, n0n odorous and "non-tacky, having a sinface coating which will not be substantially loosened when subjected to water for a substantial period of time by impregnating said sheets or films with asoftener which is preferably insoluble in water, but soluble in or wetted by one or more of the compor'ients of the solvent mixture used in the sure application of the surface coating composition.

It is, therefore, anobject of this invention to provide a method of preparing sheets or films state for a substantial petissue for achieving vMore particularly. 7

'resistanttothe of the origin composition,

* surface coating not of regenerated cellulose having a surface coatin: whereby aid-sheets or films are rendered substantially'resistant to the passage or penetration of moisture and water vapor therethrough, and

is not loosened by water 6 period of time.

Another object of this invention is to provide a method of preparing sheets or films of regenerated cellulose having a surface coating, whereby said sheets or films are rendered substantially l0 passage or penetration of moisture and water vapor therethrough and said surface coating is no loosened by water for a substantial period of time by incorporating in thesheets or films of regenerated cellulose a sof- 15 tener, said softener being soluble in or wetted by one or more of the ingredients comprising the composite solvent of the surface coating composition.

A further object of this invention comprises 20 impregnating a sheet or film of regenerated cel-, lulose in the gel or undried state with a softener prior to the application of the surface coating said softener being soluble in or wetted by the solvent mixture of the surface 25 tion.

coating composi An additional object of this invention. is to V provide a method of preparing sheets or films of.

enerated reg cellulose having a'surface coating, whereby said films ,or sheets are rendered substantially resistant to the passage or penetration of moisture or water vapor therethrough, said being loosened by water for of time, which comprises reof the water and/or watersoluble softener present in said sheets or films prior to the incorporation of the softener and the applicationof the surface coatingcompositlon. Other objects will appear from the following description and appended claims. 40 A In the manufacture of sheets or films of regenerated cellulose a solution of viscose is ejected from a hopper into a coagulating bath, whereby a continuous film of material is obtained. The coagulated film is then regenerated. If desired, the coagulating and regenerating steps may be carried out simultaneously. Subsequently, the film is washed, desulphured, bleached, again washed, and dried. Prior to the drying and while the film is still in the gel state, it is usually impregnated with glycerin whereby added flexibility and suppleness are imparted to the film. Finally, the film is cut into sheets of the desired sizes. If the sheets are to be of the variety which resists the passage and penetration of moisture and asubstlmtial moving'all or part resin, a wax and a plasticizer dissolved water vapor therethrough, the film or sheet may be treated with a composition of matter comprising, for example, a cellulose derivative, a sum or in suitable solvents or mixtures thereof with or without diluents. The coated material is then dried at a temperature substantially equal to or higher than the melting point of the wax employed in the coating composition.

As above explained, this surface coating be: comes loosened from the base when it contacts with water for a long period of time. I have found that, if the common water-soluble softener (glycerin) is removed and the film impregnated with a softener which is insoluble in water' and soluble in the solvent of the surfacing composition prior to the application of the surface coating, a satisfactorily-adhering surface coating will be produced, said coating effectively resisting the efiectsof water for a substantial period of time. In carrying out the invention, various modes of procedure may be used. The most practical procedure is to start with a cellulose film which has been coagulated, regenerated, washed, desulphured and bleached, but which has not been glycerinated or dried. At this stage the film is still in a gel state and contains a considerable amount of water. The water is removed by. extraction with a solvent miscible with water,,for example, alcohol, and the last traces of the alcohol are removed with a solvent miscible with the alcohol and also miscible with the solvents contained in the moistureproofing composition. The sheet, thus free from the water which was associated with it, is impregnated withpne of the softeners which is insoluble in waterand soluble in the solvent of the moistureproofing composi-- tion. As an alternative, the water could be' removed from the gel film by the usual process of drying.

It is not, of course, absolutely necessary to remove the water from the fihn before the impregnation with' the softener, and by the suitable choice of a softener material, this matter can be impregnated in the cellulose by means of an emulsion or a suspension. The cellulose film, having been washed and purified, is passed through an aqueous bath containing a suspension or emulsion of a softener which is insoluble in water but soluble in the solvents of the moistureproofing composition, and the filmso impregon to the usual drying mechanism wherein the water is evaporated, leaving the softener uniformly impregnated throughout the film. The film, having been impregnated, can then be coated wtih the moistureproofing composition.

It is obvious that the process is equally applicable to dried sheets or films of regenerated cellu lose produced in the ordinary course of manufacture and containing glycerin incorporated therein. Such sheets or films are treated for the removal of the glycerin and water by a process such as that which has been described; namely, av series of extractions with solvents which are miscible with the water and glycerin followed by extractions with the solvents which are soluble in the solvents of the moistureproofing composition and miscible with the first solvent. An obvi-- ous alternative of this is to remove the glycerin with a common water-wash and to impregnate the cellulose film with a suspension of the waterinsoluble softener in water followed by the usual drying.

The softeners incorporated in the sheets or films of regenerated cellulose, as above-menas tri-cresyl phosphate,

the surface coating comprises, as previously stated, a

' ester gum, resin,

tia lly cresyl phosphate, triphenyl phosphate, diamyl tioned, are water insoluble and are soluble inor wetted by the solvents of the moistureproofing composition. I have found that such softeners trfacetin, and dibutyl tartrate are particularly suitable. The degree of 5 suppleness and flexibility of the final product depends, of course on the amount of softener which is incorporated in the film. I I

The composition which may be employed for l0 cellulose derivative, a gum or resin, a wax, a plasticizer and a solvent or solvent mixture.

The cellulose derivatives may be nitrocellulose, cellulose acetate or cellulose 'ether and the like. The. gum or resin which may be used may be gum-mastic, copal resins or syn- These gums orresins may be used or in combination with one antic resins.

er separately other.-

For the wax, high melting-point paraflln wax is preferable. Other waxes, such as beeswax. carnauba wax, ceresin wax and the like, or a combination thereof, may be used.

The plasticizer which may be employed comth ei prises any of the compounds or mixtures having a, high boiling point and which are known as -plasticizers" or softeners for cellulose derivatives. Preferably, a plasticizer which is substancolorless and odorless is desirable. Triphthalate, dibutyl phthalate and castor oil have produced satisfactory results.

The above ingredients, when used in proper proportions and with a suitable solvent or solvent mixture, p roduce a material which, after evap-. oration of the solvent, is not only resistant to' the passage or penetration of moisture and water vapor therethrough, but is flexible without cracking, perfectly transparent, devoid of greasiness 40 or tackiness, and has the required, tensile strength for which it is desired to be used.

Various proportions of the above ingredients may be used. Satisfactory results have been obtained when the ingredients are used in the following percentages byweight:

' Per cent Cellulose derivative 30-70 Gum 20-60 Wax 2-10 Plasticizer 5-30 The following specific example produces the desired results:

. The wax and cellulose derivative base ordinarily do not mix to form a clear transparent However, by a proper choice of gum, it has been found possible to make the combined gum and wax mix with the plasticizer and cellulose derivative. The solvent mixture is then chosen to retain the gum, wax, cellulose derivav tive and plasticizer in their proper proportions in completesolution until the entire solvent has evaporated.

It is desirable to ingredients to maintain employ solvents for the abbve up to.50% or over by weight in order the wax in solution during the process of drying the coating or sheet. Also, itis desirable to employ relatively low percentages of intermediate boiling solvents for the cellulose derivative. By employing these solvents in a proportion of 10% and under of the total solvent, a very rapid drying of the coating is prevented. While the particular solvent must be determined separately for the particular composition, I have found that the following specific solvent combination, when used with the above example, produces satisfactory results:

In order to more clearly explain the invention, the following specific examples are set forth. It is to be understood that these ingredients are not limitative of the invention but merely describe certain modifications thereof:

Example I.--100 cc. of tri-cresyl phosphate, 30 cc. oi oleic acid and a small quantity of water are mixed thoroughly agitated. agitated, 8 cc..oi solution diluted with water is a little 28% ammonia added and the agitation continued for while until the dispersion or em tially complete. Sufllcient water is then added to make apprommately 2200 cc.

Into the composition prepared, as above defilm of regenerated cellulose which has not been dried and which is in its gel composition; the excess any suitable manner. The him is then dried at approximately C., and after dry the him is coated with the moistureproofing compocellulose derivative, or a resin, a wax, and a plasticizer, and jected to a temperature approximately the same as, or higher than, the melting point of the wax employed in the moistureprooi composition. if desired, the coated sheet may he subiected to a humidifying atmosphere whereby the final product's flexibility may be increased. Example IL-A sheet or filmoi regenerated cellulose which hasnot been dried and which is in a gel state is treated with alcohol to remove the water associated with the cellulose. After several washings with 95% alcohol, the cellulose is finally treated with toluene to remove the last traces'of the alcohol. The sheet is then ersed in a 10% solutionof kl-343651 1 phosphate in toluene. The excess solution is removed and the solvent evaporated. The film is then coated with the moistureproofing composition, and. finished as set forth inple I.

Emplc l'lL-A sheet of regenerated cellulose, which has been impregnated with glycerin and has been dried is immersed in 95% alcohol, and is repeated until substantially all of the glycerin and water have been rmoved irom the cellulose. The surplus alcohol is removed in any suitable manner, and the dim. is'immersed in a 2% solution of triacetin in 95% alcohol. After the removal oi the excess liquid, the him is dried and then coated with the moistureprooiing composition and finished as set forth in Example I.

The product resulting from the herein-describedmethod comprises a sheet or film of regenerated cellulose having a moistureproof coatulsion is suhstanby said water-insoluble softener,

ether, said article being transparent,

ing, comprising a cellulose derivative, 9. gum or resin. a wax and a plasticizer It is perfectlytranspar t, non-odorous, non-tacky and resist ant to the e of water vapor and moisture. therethrough to a substantial degree. .In addition, the moistureproof surface coating adheres to the base and when exposed in contact ,with water, it does not loosen therefrom for a substantial period of time.

The expression resistant to the passage or penetration of moisture or water vapor" is intended to include also that property described by the term moistureproof", by which is meant the ability to resist the diilusion of water vapor to an extent at least as great as or exceeding papers emplayed as wrappers and functioning to resist the time, depending on the and/or being approximately '7 times or more as effective as uncoated sheets or films of regen= erated cellulose when tested in accordance with the test set iorth in the Journal of industrial and Engineering Chemistry on page 6 (June 1929)..

Since it is obvious that various changes may be made in the specific details above set forth, it is to be understood that this invention is not limited thereto except as set forth pended claims.

I claim: 1. An article of ma ufacture comprising a sheet or film of regenerated cellulose impregnated with a composition consisting insoluble softener for regenerated cellulose and combined with a moistureproofing composition rendering said article moistureprcoii, said mole-- tureproofing composition'being bonded to the base log out, flexihleand non-tacky.

2. an article or manufacture comprising a sheet or film of regenerated cellulose impregnated with a'composition consisting essentially of a for regenerated cellua5 water-insoluble softener lose and having a surface coating of a moisture proofing composition, said surface coating being handed to the base by said water-insoluble softnon-tacw.

3. An article of manufacture comprising a sheet or oi regenerated cellulose impregnated with a composition consisting essentially of a water-insoluble softener for regenerated cellulose moisturep'roof comprising a cellulose derivative, a a wax and a. plasticizer, said surface coating being bonded to $118 base by said water lnsoluble softener, said article being transparent, eem.

c. an article of manufacture comprising a sheet or him of regenerated cellulose impregnatedwlth a composition consisting essentially oil a water-insoluhlesoitenertor regenerated cellulose 1 selected from the cresyl phosphate, tartrate and having a surface coating of a moistureprooiing composition rendering said article resistant to the passage or penetration of moisture and water vapor therethrough, said article being t w 2 7 phosphate and combined with a moistureprooflng 75 575, vol. 21, No. 25.

in the ap- 30 essentially of a water- 35 said article beso flexible and sin-face coating 55 flexible and mom of a trid5 composition rendering the article resistant to the passage or penetration of moisture and water vapor therethrough,said article being transparent, flexible and non-tacky.

6. An article of manufacture comprising asheet or film of regenerated cellulose impregnated with a composition consisting essentially of tricresyl phosphate and having a moistureproof sin-face coating comprising a cellulose derivative, a sum, a wax and a plasticizer, to the passage orpenetration of moisture and water vapor therethrough, transparent,'flexible and non-tacky.

-7. In a method of transparent and flex cellulose in the undried state with a composition consisting essentially of tricresyl phosphate and a liquid vehicle, removing the excess of said composition, drying said treated applying a moistureprooflng coating composition comprising a cellulose derivative, a gum, a wax, a plasticizer and a solvent, said tricresyl phosphate being soluble in said solvent.

8. In a method of preparing a moistureproof,

transparent and flexible material, the steps which orfllm of regenerated cellulose in the undried state with a composition consisting of tricresyl phosphate dispersed in a liquid vehicle, removing the excess of the dispersion, drying said treated sheet or fllm, and applying. a moistureproofing coating composition comprising a cellulose derivative, a gum, a wax, a plasticizer and a solvent, said tricresyl phosphate being soluble in said solven 9. In a method of preparing a moistureproof,

' transparent and flexible material, the steps which comprising tricresyl phosphate, removing the excess of said dispersion and drying said treated sheet or fllm and applying a surface coating composition to render the material resistant to the passage or penetration of moisture or water vapor therethrough, said composition containing a solvent in which the tricresyl phosphate is soluble.

10. In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting, the steps which comprise impregnating regenerated cellulose sheeting with a composition consisting of a water-insoluble softener for regenerated cellulose dispersed in an aqueous medium, and applying a moistureprooflng composition containing a solvent in which said softener is soluble to produce a transparent moistureproof surface coating bonded to the base sheeting.

11. In a method of preparing transparent, flexible and .moistureproof regenerated cellulose sheeting which comprises producing transparent regenerated cellulose sheeting in the gel state,

impregnating the sheeting with a composition consisting of a water-insoluble softener for regenerated cellulose dispersed in an aqueous mediu m, and applying a moistureprooflng composition containing a solvent in which said softener is soluble to produce a transparent moistureproof surface coating bonded to the base sheeting.

' 12, In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting, the steps which comprise impregnating regenerated cellulose sheeting with a composition consisting of a'water-insoluble. softener for regenerated cellulose dispersed in anaqueous medlum, said softener being selected from the class said article being resistant regenerated cellulose sheet or fllm, and v which consists of tricresyl phosphate, triacetin and dibutyl tartrate, drying the impregnated sheeting, and applying a moistureprooflng composition containing a solvent in which said softener is soluble to produce a transparent moistureproof surface coating bonded to the base sheeting.

13. In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting which comprises producing transparent sheeting in the gel state, impregnating the sheeting with a. composition consisting of a. water-insoluble softener for regenerated cellulose dispersed in an aqueous medium, said softener being selected from the class which consists of tricresyl phosphate, triacetin and dibutyl tartrate, drying the impregnated sheeting, and applying a moistureprooiing composition containing a solvent in which said softener is soluble to produce -a transparent moistureproof surface coating bonded to the base sheeting.

14. In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting, the steps which comprise impregnating regenerated cellulose sheeting with a. composition consisting essentially of a water-insoluble softener for regenerated cellulose selected from the class-which consists of tricresyl phosphate, triacetin and dibutyl tartrate, and applying a. moistureproofing surface coating composition containing a solvent in which said softener is soluble.

15. In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting, the steps which comprise producing a consists of tricresyl phosphate, triacetin and dibutyl tartrate, drying the impregnatedsheeting,

and applying a moistureprooflng surface coating composition containing a solvent inwhich said softener is soluble. I

1'7. In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting which comprises producing transparent regenerated cellulose sheeting in the gel state, removing the water by solvent displacement, impregnating, the sheeting with a solution consisting essentially of a ated cellulose selected from the class which consists of tricresyl phoop "te, triacetin and dibutyl tartrate, drying the impregnated sheeting, and applying a moistureproofing surface coating composition containing a solvent in which said softener is soluble.

18. In a method ofpreparing transparent, flexible and moistureproof regenerated cellulose sheeting, the steps which comprise impregnating regenerated cellulose sheeting with'a composition consisting essentially of a water-insoluble sofsolvent having dissolved therein a water-insoluble softener for regenertener for regenerated cellulose and applying a moistureproofing composition containing a solvent' in which said softener is 'soluble to produce a transparent, moistureproof surface coating bonded to said base.

19. In a method of preparing transparent, flexible and moistureproof regenerated cellulose sheeting, the steps which comprise producing a transparent regenerated cellulose in the gel state,

removing the water by solvent displacement, im-

' pregnating the sheeting with a composition consisting essentially of a water-insoluble softener for regenerated cellulose, and applying a moistureproofing composition containing a. solvent in which said softener is soluble to produce a. transparent moistureproof surface coating bonded to said base.

. JOHN C. SIEMANN.

CERTIFICATE OF CORRECTION.

Patent No. 2,042,658. I Q I 4 June 2,1956.

JOHN G. SI EMAN N.

It is herehy certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 56, for "wtih" read with; page 3, second column, after line 26,' insert the following paragraphs:

In the above description the expression "sheets or films of regenerated cellulose" is used. It is to be understood that this expression is not limited to any particular type or species but is intended to cover sheets or films of regenerated cellulose of any manufacture including cellulos'i-c sheets or films in which a portion thereof has been gelatinized and/or regenerated.

In the claims the term "solvent" is intended to also include a composite. solvent or a solvent mixture containing one or more ingredients which dissolves and/or wets the softener.

and that the said Letters Patent should be read with these corrections I therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 4th day of August, A. D. 1956.

Henry Van Aredale (Seal) Acting Commissioner of Patents. 

